KR101360461B1 - Asymmetric Mono or Di Antracene Derivertives and Organic EL Element Using the Same - Google Patents

Abstract

The present invention relates to an asymmetric mono or dianthracene derivative having an adamantane group, a material for an organic electroluminescent device containing the same, and an organic electroluminescent device using the same.

Adamantane, anthracene derivative, organic electroluminescent device, organic EL

Description

Asymmetric Mono or Di Anthracene Derivatives Having Adamantane Groups and Organic Electroluminescent Devices Using the Same

1 is a view showing the structure of a conventional organic electroluminescent device.

* Explanation of the major symbols in the drawings *

1: substrate 2: anode

3: hole injection layer 4: hole transport layer

5: light emitting layer 6: electron transport layer

7: cathode

The present invention relates to an asymmetric mono or dianthracene derivative having an adamantane group, a material for an organic electroluminescent device containing the same, and an organic electroluminescent device using the same.

An organic electroluminescent device is a self-luminous device that uses a principle that a fluorescent material emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. Organic materials have been constructed since low-voltage driving organic electroluminescent devices (CWTang, SAVanslyke, Applied Pysics Letters, Vol. 51, p. 913, 1987, etc.) by stacked devices have been reported by Eastman Kodak's Tang et al. Research on organic electroluminescent elements made of materials has been actively conducted. Tang et al. Use tris (8-hydroxyquinolinol aluminum) for the light emitting layer and triphenyldiamine derivative for the hole transport layer. Advantages of the laminated structure include improving the efficiency of injecting holes into the light emitting layer, blocking the electrons injected from the cathode to increase the generation efficiency of excitons generated by recombination, trapping excitons generated in the light emitting layer, and the like. Can be mentioned. As the device structure of the organic electroluminescent device as in this example, a two-layer type of a hole transport (injection) layer, an electron transport light emitting layer, or a three-layer type of a hole transport (injection) layer, a light emitting layer, and an electron transport (injection) layer is well known. . In order to increase the recombination efficiency of injected holes and electrons, device structure and formation methods have been studied.

Moreover, as a light emitting material, light emitting materials, such as a chelate complex, such as a tris (8-quinolinolato) aluminum complex, a coumarin derivative, a tetraphenyl butadiene derivative, a bis styryl arylene derivative, and an oxadiazole derivative, are known. From these, it has been reported that light emission in the visible region from blue to red is obtained, and the realization of a color display element is expected (for example, Japanese Patent Application Laid-Open No. 1996-239655 and Japanese Patent Application Laid-Open No. 195-138561). Japanese Patent Publication No. 1991-200289, etc.).

In addition, a device using a phenylanthracene derivative as a light emitting material is disclosed in Japanese Patent Laid-Open No. 1996-012600. Although such anthracene derivative is used as a blue light emitting material, it is desired to extend the device life. A material having a naphthyl group at the 9,10 position of anthracene is disclosed in Japanese Patent Laid-Open No. 1999-3782, and a device material having a fluoranthene group at the 9,10 position of Anthracene is disclosed in Japanese Patent Laid-Open No. 2001-257074. It is disclosed in the publication. Although these anthracene derivatives are also used as blue light emitting materials, improvement in device life is still desired. In addition, Japanese Unexamined Patent Publication No. 2000-182776 discloses the use of various anthracene derivatives as hole transport materials. However, evaluation as a light emitting material has not been made yet.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly endeavored to solve the problems of the prior art as described above. When the asymmetric mono or dianthracene derivative having an adamantane group is used as the material for the organic electroluminescent device, the organic electroluminescence with high luminous efficiency and long lifespan is provided. It discovered that an element was obtained and completed this invention.

Accordingly, an object of the present invention is to provide an asymmetric mono or dianthracene derivative having an adamantane group, an organic electroluminescent device material containing the same, and an organic electroluminescent device having a high luminous efficiency and long life using the same.

The present invention, in order to achieve the above object,

Asymmetric mono or dianthracene derivatives having an adamantane group represented by the following formula (1);

An organic electroluminescent device material containing the asymmetric mono or dianthracene derivative having the adamantane group; And

In an organic electroluminescent device in which one or more organic thin film layers including a light emitting layer are sandwiched between a cathode and an anode, at least one of the organic thin film layers contains an asymmetric mono or dianthracene derivative having the adamantane group. An electroluminescent device is provided.

Where

Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group having 4 to 50 nuclear carbon atoms, hydrogen, or an alkyl group having 1 to 10 carbon atoms;

In the case where Ar1 and anthracene groups substituted with Ar2 and R1 to R8 have the same structure, the positions at which they are bonded to the phenyl group are asymmetric about Ar1 and Ar2 and R2 to R8 substituted with an anthracene group around the adamantane and phenyl group. Confined to a position;

R 1 to R 8 are each independently a hydrogen atom, a substituted or unsubstituted aromatic carbon group having 6 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted carbon atom having 3 to 50 carbon atoms. Cycloalkyl group, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted Arylthio having 5 to 50 nuclear atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or unsubstituted silyl group, carboxyl group, halogen atom, cyano group, nitro group, Or a hydroxyl group.

Wherein at least one of Ar 1 and Ar 2 is an aromatic hydrocarbon group.

Substituted or unsubstituted aromatic hydrocarbon groups having 4 to 50 nuclear carbon atoms in the definition of Ar 1 and Ar 2 include, for example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 10- (1-naphthyl) -9-anthryl, 10- (2-naphthyl) -9-anthryl, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl Group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-bi Phenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group , m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4 -Methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4'-methylbiphenylyl group, 4 ''-t-butyl-p-terphenyl-4-yl group, m-terphenyl-5 ' -Yl, 4- (2,2-diphenylethenyl) phenyl group, etc. are mentioned,

Among these, a phenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 10- (1-naphthyl) -9-anthryl, 10- (2-naphthyl) -9-anthryl, 1- Naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, o -Tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, m-terphenyl-5'-yl, 4- (2,2-diphenylethenyl) phenyl group, etc. are preferable.

Regarding the asymmetric structure of the compound of Formula 1, in other words, Ar 1 bonded to a phenyl group in Formula 1, and an anthracene group substituted with Ar 2 and R 1 to R 8 may be bonded to a position symmetric with respect to a phenyl group and an adamantane group In this case, they must have different structures from each other, and Ar1 and Ar2 and anthracene groups substituted with Ar2 and R1 to R8 may have the same structure only when they are not bonded at symmetrical positions. Therefore, mono or dianthracene derivatives having adamantane groups in the present invention will always have an asymmetric structure.

Specific examples of the asymmetric mono or dianthracene derivatives having an adamantane group represented by the formula (1) include compounds represented by the following formulas (2) and (3). However, the scope of the compound of formula 1 is not limited to these exemplary compounds.

Compound No. Ar1 Ar2 Compound 1 Hydrogen 2-naphthyl Compound 2 Phenyl 2-naphthyl Compound 3 m-terphenyl-5'-yl 2-naphthyl Compound 4 4- (2,2-diphenylethenyl) phenyl 4- (2,2-diphenylethenyl) phenyl

Compound No. Ar1 Ar2 Compound 5 10- (2-naphthyl) -9-antril 2-naphthyl

The asymmetric anthracene derivative having an adamantane group of the present invention prepares a halobenzene in which adamantane is substituted by a Friedelcraft reaction of an adamantane derivative prepared by halogenation with halobenzene, and a known method is Suzuki Couple. It can synthesize | combine using ring reaction, a halogenation reaction, and a boration reaction suitably.

The method for preparing an asymmetric mono or dianthracene derivative having an adamantane group represented by Formula 1 of the present invention can be illustrated by the following schemes. However, the following reaction schemes do not limit the method for producing an asymmetric mono or dianthracene derivative having an adamantane group of the present invention.

The synthesis method of Compound 2 is described in more detail as in Scheme 2 below.

Synthesis method of Compound 4 exemplified above as a compound of Formula 1 is represented by the following scheme.

In the case of the asymmetric mono or dianthracene derivative having adamantane represented by the general formula (1) in the present invention, 1,3-bromoa is not limited to using 1-monobromo adamantane as a starting material. However, even if the starting material is tan, 1,3,5-tribromo adamantane, or 1,3,5,7-tetrabromo adamantane, halobenzene is substituted by adamantane through Friedelcraft reaction. It is possible to prepare and from this synthesize asymmetric anthracene derivatives with adamantane. In addition, halobenzenes that perform Friedelcraft reactions with adamantane derivatives are not limited to 1,3-dibromo benzene and 1,4-dibromo benzene, but may also be prepared by Friedelcraft reaction using Lewis acid. Any kind of benzene containing two or more identical or different halogen atoms may be used.

In the above, Suzuki coupling reaction has been made up of many reports so far (documents 'Chem. Rev., Vo 1.95, No. 7, 2457 (1995)', etc.), and can be carried out under the reaction conditions described therein. The reaction is usually carried out under an inert atmosphere such as nitrogen, argon, helium and the like under normal pressure, but may be carried out under pressurized conditions as necessary. Although reaction temperature is the range of 15-300 degreeC, Especially preferably, it is 30-200 degreeC.

Examples of the halogen used for the halogenation include iodine atoms, bromine atoms, chlorine atoms and the like, and are preferably iodine atoms and bromine atoms. Although the halogenating agent in a halogenation reaction is not specifically limited, For example, N-halogenation succinimide is used suitably. The reaction is usually carried out in an inert solvent under an inert atmosphere such as nitrogen, argon or helium. As an inert solvent used, for example, N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone, dimethyl sulfoxide, carbon tetrachloride, chlorobenzene, dichlorobenzene, nitro Benzene, toluene, xylene methyl cellosolve, ethyl cellosolve, water, etc. are mentioned, Preferably, they are N, N- dimethylformamide and N-methylpyrrolidone.

The boration reaction can be carried out by a known method (Japanese Chemistry Part, Experimental Chemistry Lecture No. 4, vol. 24, pages 61 to 90, and J. Org.Chem., Vol. 60, 7508 (1995), etc.). Do.

The organic electroluminescent device material of the present invention contains an asymmetric mono or dianthracene derivative having an adamantane group represented by the formula (1), and is preferably used as a light emitting material or a host material.

The organic electroluminescent device of the present invention is an organic electroluminescent device in which an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, wherein at least one of the organic thin film layers is represented by Formula 1 above. It is characterized by containing an asymmetric mono or dianthracene derivative having an adamantane group represented by one or two or more kinds thereof.

The organic electroluminescent device of the present invention preferably contains an asymmetric mono or dianthracene derivative having an adamantane group represented by the formula (1), and more preferably used as a main component.

Hereinafter, the structure of the organic electroluminescent element of this invention is demonstrated.

The organic electroluminescent device according to an embodiment of the present invention may include a substrate, an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode. The electron injection layer may be further included between the electron transport layer and the cathode, and the hole injection layer may be further included between the anode and the hole transport layer.

The aforementioned organic thin film layer means a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.

Examples of the anode material include metal oxides or metal nitrides such as ITO, IZO, tin oxide, zinc oxide, zinc aluminum oxide, and titanium nitride; Metals such as gold, platinum, silver, copper, aluminum, nickel, cobalt, lead, molybdenum, tungsten, tantalum and niobium; An alloy of such a metal or an alloy of copper iodide; Conductive polymers such as polyaniline, polythiopine, polypyrrole, polyphenylenevinylene, poly (3-methylthiopine), and polyphenylenesulfagard. The anode may be formed of only one type of the above materials or may be formed of a mixture of a plurality of materials. In addition, a multilayered structure composed of a plurality of layers of the same composition or different composition may be formed.

The hole injection layer of the present invention may use materials known in the art, but is not limited to PEDOT / PSS or copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine A material such as (m-MTDATA) is formed to a thickness of 5 nm to 40 nm.

The hole transport layer may be 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (NPD) or N, N'-diphenyl-N, N'-bis (3- A substance such as methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD) can be used.

The light emitting layer may use materials known in the art, and such materials are not limited to, but are not limited to (4,4'-bis (2,2-diphenyl-ethen-1-yl) diphenyl (DPVBi), bis ( Styryl) amine (DSA), bis (2-methyl-8-quinolinolato) (triphenylsiloxy) aluminum (III) (SAlq), bis (2-methyl-8-quinolinolato) ( Para-phenolato) aluminum (III) (BAlq), bis (salen) zin (II), 1,3-bis [4- (N, N-dimethylamino) phenyl-1,3,4-oxadiazolyl] Benzene (OXD8), 3- (biphenyl-4-yl) -5- (4-dimethylamino) -4- (4-ethylphenyl) -1,2,4-triazole (p-EtTAZ), 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ), 2,2 ', 7,7'-tetrakis (non- Phenyl-4-yl) -9,9'-spirofluorene (Spiro-DPVBI), tris (para-ter-phenyl-4-yl) amine (p-TTA), 5,5-bis (dimethytilboyl ) -2,2-bithiophene (BMB-2T) and perylene.

Tris (8-quinolinato) aluminum (III) (Alq3), DCM1 (4-dicyanomethylene-2-methyl-6- (para-dimethylaminostyryl) -4H-pyran), DCM2 (4- Dicyanomethylene-2-methyl-6- (zulolidin-4-yl-vinyl) -4H-pyran), DCJT (4- (dicyanomethylene) -2-methyl-6- (1,1,7, 7-tetramethylzulolidil-9-enyl) -4H-pyran), DCJTB (4- (dicyanomethylene) -2-tertbutylbutyl-6- (1,1,7,7-tetramethylzololidyl -9-enyl) -4H-pyran), DCJTI (4-dicyanomethylene) -2-isopropyl-6- (1,1,7,7-tetramethylzulolidil-9-enyl) -4H-pyran ) And nile red, rubrene, etc. can be used as a host or dopant.

Dopants may be omitted or optionally added, but are not limited to those listed as host materials above.

The electron transport layer may include an aryl substituted oxadiazole, an aryl-substituted triazole, an aryl-substituted phenanthroline, benzoxazole, or a benzisazole compound, for example, 1,3-bis ( N, Nt-butyl-phenyl) -1,3,4-oxadiazole (OXD-7); 3-phenyl-4- (1'-naphthyl) -5-phenyl-1,2,4-triazole (TAZ); 2,9-dimethyl-4,7-diphenyl-phenanthroline (basocuproin or BCP); Bis (2- (2-hydroxyphenyl) -benzoxazolate) zinc; Or bis (2- (2-hydroxyphenyl) -benziazolate) zinc; As the electron transporting material, (4-biphenyl) (4-t-butylphenyl) oxydiazole (PDB) and tris (8-quinolinato) aluminum (III) (Alq3) can be used, preferably Tris ( Preference is given to 8-quinolinato) aluminum (III) (Alq3).

The electron injection layer and the cathode may use a material known in the art, but is not limited to LiF as an electron injection layer and a metal having a low work function such as Al, Ca, Mg, Ag may be used as the cathode. Al is preferred.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited thereto.

In the following examples, intermediates 1 to 8 mean those described in Scheme 4 below.

Example  1: Synthesis of compound 1

1-monobromoadamantane (20.0g) and tribromoaluminum (3.0g) as a catalyst were put in 1,3-dibromobenzene solvent (80g) and kept at 0 ~ 5 ℃ using an ice-bath. Friedelcraft reaction through 13-hour stirring synthesized 1- (3,5-dibromo-phenyl) -adamantane (Intermediate 1: 21.9 g) as a white solid. The intermediate 1 (5.0 g) and 1.6 M n-BuLi (8.8 mL) were stirred for 30 min in a bath of -70 to -80 ° C in anhydrous tetrahydrofuran solvent (150 mL), followed by lithium-halogen exchange reaction. The reaction was terminated with 1- (3-bromo-phenyl) -adamantane (Intermediate 2: 3.2 g). This intermediate 2 (2.5 g) and 9-anthraceneboronic acid (1.9 g) were added to 1,2-dimethoxymethane (hereinafter, DME) solvent (25 mL), followed by Pd catalyst (0.6 g) and a 2M aqueous solution of sodium carbonate (12.5 mL). Suzuki coupling reaction under reflux for 14 hours under) gave 1- (3-anthracene-9-yl-phenyl) -adamantane (Intermediate 3; 1.6 g). The obtained intermediate 3 (1.6 g) was added with 0.8 g of NBS in dimethylformamide (hereinafter referred to as DMF) solvent (20 mL) and brominated by stirring at room temperature for 4 hours to thereby obtain 1- [3- (10-bromo-anthracene). -9-yl) -phenyl] -adamantane (intermediate 4; 1.5 g), and intermediate 4 (1.5 g) in 0.25 g of Pd catalyst [Tetrakis (triphenylphosphine) Palladium (0)] in DME solvent (20 mL). After adding 1 equivalent (0.6 g) of 2-naphthyl boronic acitic acid, 2 M aqueous sodium carbonate solution (10 mL) was added to the desired 1- [3- (10-naphthalene-) as a Suzuki coupling reaction through reflux for 10 hours. 2-yl-anthracene-9-yl) -phenyl] -adamantane (Compound 1: 1.0 g) was obtained. Subsequently, sublimation purification secured a blue light emitting material required for device fabrication.

Yellow solid: ¹ H NMR (CDCl ₃ , 300 MHz) δ 1.77 (m, 6H), 2.02 (m, 6H), 2.11 (m, 3H), 7.32 (m, 4H), 7.46 (m, 2H), 7.49 (m, 1H), 7.55 (m, 2H), 7.59 (m, 2H), 7.65 (m, 1H), 7.70 (d, 1H), 7.73 (m, 1H), 7.75 (d, 1H), 7.92 ( m, 1H), 7.98 (d, 1H), 8.03 (t, 1H), 8.08 (d, 1H)

Example  2: Synthesis of Compound 2

Using the same method as in Example 1, tribromoaluminum as a catalyst with 1-monobromoadamantane was added to a 1,3-dibromobenzene solvent, and then 1- (3,5-dibromo was reacted through a Friedelcraft reaction. -Phenyl) -adamantane (intermediate 1) was synthesized. This intermediate 1 (11.0 g) was subjected to halogen-halogen exchange reaction with 19.5 mL of 1.6 M n-BuLi and I ₂ (8.7 g) in anhydrous tetrahydrofuran solvent (440 mL) to give 1- (3-bromo-5 Iodine-phenyl) -adamantane (intermediate 5: 9.9 g) was synthesized. This intermediate 5 (9.9 g) and 9-anthracene boronic acid (5.3 g) were added to a DME solvent (100 mL), followed by addition of a Pd catalyst (1.7 g) and a 2 M aqueous sodium carbonate solution (50 mL), followed by Suzuki coupling. 1- (3-Anthracene-9-yl-5-bromo-phenyl) -adamantane (Intermediate 6: 6.7 g) was obtained. Intermediate 6 (3.7 g), phenylboronic acid (0.96 g), Pd catalyst (0.55 g) and 2M aqueous sodium carbonate solution (20 mL) were added under a DME (40 mL) solvent to give a Suzuki coupling reaction. Anthracene-9-yl-biphenyl-3-yl) -adamantane (Intermediate 7: 2.6 g) was obtained, followed by bromination with NBS (2.0 g) in DMF (30 mL) solvent. The 1- [5- (10-bromo-anthracene-9-yl) -biphenyl-3-yl] -adamantane (intermediate 8: 2.4 g) obtained therefrom was subjected to Pd catalyst ( 0.32 g) was used to add 1 equivalent (0.76 g) of 2-naphthylboronic acid sheet and 2 M aqueous sodium carbonate solution (10 mL) to the desired 1- [5- (10-naphthalen-2-yl-anthracene-9-yl ) -Biphenyl-3-yl] -adamantane (Compound 2; 1.6 g) was obtained. Subsequently, sublimation purification secured a blue light emitting material required for device fabrication.

Yellow solid: ¹ H NMR (CDCl ₃ , 300 MHz) δ 1.80 (m, 6H), 2.09 (m, 6H), 2.13 (m, 3H), 7.32 (m, 5H), 7.46 (t, 2H), 7.51 (m, 1H), 7.61 (m, 4H), 7.72 (m, 4H), 7,78 (t, 1H), 7.82 (m, 1H), 7.84 (d, 1H), 7.93 (m, 1H), 7.99 (s, 1 H), 8.04 (m, 1 H), 8.09 (d, 1 H)

Example  3: Synthesis of Compound 3

Compound 3 was obtained in the same manner as in Example 2, except that terphenylboronic acid was used instead of the phenylboronic acid in the intermediate synthesis step of Example 2. Subsequently, sublimation purification secured a blue light emitting material required for device fabrication.

Yellow solid: ¹ H NMR (CDCl ₃ , 300 MHz) δ 1.80 (m, 6H), 2.10 (m, 6H), 2.14 (m, 3H), 7.32 (m, 2H), 7.38 (m, 5H), 7.47 (m, 4H), 7.56 (dd, 1H), 7.61 (m, 3H), 7.72 (m, 7H), 7.79 (m, 1H), 7.83 (m, 1H), 7.86 (m, 2H), 7.89, (d, 2H), 7.99 (s, 1H), 8.03 (m, 1H), 8.08 (dd, 1H)

Example  4: Synthesis of Compound 4

Using the same method as in Example 1, tribromoaluminum as a monomonobroadamantane and a catalyst was added to a 1,3-dibromobenzene solvent, and the 1- (3,5-dibromo reaction was performed through a Friedelcraft reaction. -Phenyl) -adamantane (intermediate 1) was synthesized. This intermediate 1 (5.5 g) was subjected to halogen-halogen exchange reaction in anhydrous tetrahydrofuran solvent (220 mL) with 9.8 mL of 1.6 M n-BuLi and I ₂ (4.9 g) to give 1- (3-bromo-5 Iodine-phenyl) -adamantane (intermediate 5; 5.0 g) was synthesized. This intermediate 5 (5.0 g), 9-anthraceneboronic acid (2.7 g), Pd catalyst (0.85 g), and 2M aqueous sodium carbonate solution (25 mL) were added to a DME solvent (50 mL) to conduct a Suzuki coupling reaction. (3-Anthracene-9-yl-5-bromo-phenyl) -adamantane (intermediate 6; 3.4 g) was obtained. The obtained intermediate 6 (3.4 g) was brominated with NBS (2.6 g) in a DMF solvent (40 mL) and stirred at room temperature for 4 hours to give 1- [3-bromo-5- (10-bromo- Anthracene-9-yl) -phenyl] -adamantane (3.2 g) was obtained, and 1- [3-bromo-5- (10-bromo-anthracene-9-yl) -phenyl] -adamantane ( 3.2 g) was added with 2 equivalents of 4- (2,2-diphenyl-vinyl) -bronic acid (3.5 g) and 2M aqueous sodium carbonate solution (20 mL) using a Pd catalyst (0.85 g) in a DME solvent (40 mL). , 1- [4 '-(2,2-diphenyl-vinyl) -5- {10- [4- (2,2-diphenyl-vinyl) -phenyl as a Suzuki coupling reaction via reflux for 14 hours ] -Anthracene-9-yl} -biphenyl-3-yl] -adamantane (Compound 4; 2.6 g) was obtained. Subsequently, sublimation purification secured a blue light emitting material required for device fabrication.

Yellow solid: ¹ H NMR (CDCl ₃ , 300 MHz) δ 1.77 (m, 6H), 2.03 (m, 6H), 2.10 (m, 3H), 7.00 (s, 1H), 7.06 (s, 1H), 7.09 (s, 1H), 7.15 (s, 1H), 7.24 (m, 4H), 7.32 (m, 15H), 7.38 (m, 5H), 7.42 (m, 5H), 7.46 (s, 1H), 7.49 ( m, 2H), 7.72 (m 5H)

Example  5: Fabrication and Evaluation of Organic Electroluminescent Device 1

A glass substrate with an ITO transparent electrode having a thickness of 25 mm X 75 mm X 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, followed by UV ozone cleaning for 30 minutes. The glass substrate with a transparent electrode line after cleaning is mounted on the substrate holder of the vacuum deposition apparatus, and first, the transparent electrode is covered on the side of the side where the transparent electrode line is formed, and m-TDATA, which is a hole injection material, is used for resistive heating deposition. It formed into a film. NPD as a hole transport material was formed on it by the same vapor deposition method. Then, after depositing Compound 2 prepared in Example 2 to a thickness of 40nm on the light emitting layer, Alq3 was formed into an electron transport material. An Li film was formed thereon at a film thickness of 10 nm at a film formation rate of 1.5 msec / sec: 1 m / min, and Al was deposited on the Li film to form a metal cathode having a thickness of 130 nm to fabricate an organic electroluminescent device. The evaluation results are shown in Table 1.

Example  6: Fabrication and Evaluation of Organic Electroluminescent Device 2

An organic electroluminescent device was manufactured in the same manner as in Example 5, except that Compound 4 prepared in Example 4 was used instead of Compound 2. The evaluation results are shown in Table 1.

Comparative Example  1: Fabrication and Evaluation of Organic Electroluminescent Device 3

An organic electroluminescent device was manufactured in the same manner as in Example 5, except that the compound of Formula 4 was used instead of Compound 2. The evaluation results are shown in Table 1.

Current density
(mA / cm ² ) Color coordinates CIE1931
(x, y) efficiency
(cd / A) Example 5 10 (0.177, 0.158) 3.85 Example 6 10 (0.153, 0.121) 4.10 Comparative Example 1 20 (0.187, 0.218) 1.67

When the asymmetric mono or di anthracene derivative having an adamantane group represented by the formula (1) is used in the light emitting layer from the results of Table 1, the efficiency and color coordinates are higher than those of using the compound of the formula (4) containing anthracene, which is a known light emitting material It can be seen that the excellent results in the.

As described above, the organic electroluminescent device using the organic electroluminescent device material containing an asymmetric mono or dianthracene derivative having an adamantane group represented by the general formula (1) of the present invention has high luminous efficiency and long lifespan. Has For this reason, it is useful as an organic electroluminescent element by which long-term continuous use is assumed.

Claims (11)

An asymmetric mono or dianthracene derivative having an adamantane group represented by the following formula (1):

 (One) Where Ar1 and Ar2 are each independently an aromatic hydrocarbon group having 4 to 50 nuclear carbon atoms; In the case where Ar1 and the anthracene groups substituted with Ar2 and R1 to R8 have the same structure, the positions at which they are bonded to the phenyl group are asymmetric about Ar1 and the anthracene groups substituted with Ar1 and Ar2 and R1 to R8 around the adamantane and phenyl groups. Confined to a position; R 1 to R 8 each independently represent a hydrogen atom, an aromatic hetero group having 6 to 50 carbon atoms, an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 3 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, and a 6 to 50 carbon atoms. Aralkyl group, aryloxy group having 5 to 50 nuclear atoms, arylthio group having 5 to 50 nuclear atoms, alkoxycarbonyl group having 1 to 50 carbon atoms, silyl group, carboxyl group, halogen atom, cyano group, nitro Group or a hydroxyl group. delete The aromatic hydrocarbon group having 4 to 50 nuclear carbon atoms according to claim 1 is a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 10- (1-nap). Tyl) -9-anthryl, 10- (2-naphthyl) -9-anthryl, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl Group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-bi Phenylyl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o- Tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl- 1-anthryl group, 4'-methylbiphenylyl group, 4 ''-t-butyl-p-terphenyl-4-yl group, m-terphenyl-5'-yl, or 4- (2,2-di Asymmetric mono or di having an adamantane group, characterized in that it is a phenylethenyl) phenyl group Trad metallocene derivative. The aromatic hydrocarbon group of 4 to 50 nuclear carbon atoms according to claim 1, wherein a phenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 10- (1-naphthyl) -9-anthryl, 10- (2 -Naphthyl) -9-anthryl, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3 -Biphenylyl group, 4-biphenylyl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, m-terphenyl-5'-yl, or 4- (2,2-di Asymmetric mono or dianthracene derivative having an adamantane group, characterized in that it is a phenylethenyl) phenyl group. An organic electroluminescent device material comprising an asymmetric mono or dianthracene derivative having an adamantane group according to any one of claims 1, 3, and 4. The organic electroluminescent device material according to claim 5, wherein the organic electroluminescent device material is a light emitting material. The organic electroluminescent device material according to claim 5, wherein the organic electroluminescent device material is a host material. In an organic electroluminescent device in which one or more organic thin film layers including a light emitting layer are sandwiched between a cathode and an anode, at least one of the organic thin film layers is the adamantane of any one of claims 1, 3, and 4. An organic electroluminescent device containing an asymmetric mono or dianthracene derivative having a group. The organic electroluminescent device according to claim 8, wherein the organic thin film layer containing an asymmetric mono or dianthracene derivative having an adamantane group is a light emitting layer. The organic electroluminescent device according to claim 9, wherein the light emitting layer further contains a dopant compound. The compound of claim 1, wherein Ar 1 is a phenyl, m-terphenyl-5'-yl, or 4- (2,2-diphenylethenyl) phenyl group, and Ar 2 is a naphthyl or 4- (2,2-diphenyl group; Tenyl) phenyl group; R1 to R8 are asymmetric mono or dianthracene derivative having an adamantane group, characterized in that a hydrogen atom.

Images